C��lula solar de SnO2/TiO2 preparada por spray - pir��lise ativada com corante org��nico

Coordena����o de Aperfei��oamento de Pessoal de N��vel Superior (CAPES)

Polimeri tiofenici funzionali e loro applicazioni nel fotovoltaico

Recentemente, sempre pi�� attenzione �� stata rivolta all' utilizzo di coloranti organici come assorbitori di luce per la preparazione di strati fotoattivi in celle solari organiche (OPV). I coloranti organici presentano un'elevata abilit�� nella cattura della luce solare grazie all'elevato coefficiente di estinzione molare e buone propriet�� fotofisiche. Per questi motivi sono eccellenti candidati per l'incremento della conversione fotoelettrica in OPV. In questa tesi viene descritta una nuova strategia per l'incorporazione di derivati porfirinici in catena laterale a copolimeri tiofenici. Gli studi svolti hanno dimostrato che poli(3-bromoesil)tiofene pu�� essere variamente funzionalizzato con idrossitetrafenilporfirina (TPPOH), per l'ottenimento di copolimeri utilizzabili come materiali p-donatori nella realizzazione di OPV. I copolimeri poli[3-(6-bromoesil)tiofene-co-(3-[5-(4-fenossi)-10,15,20-trifenilporfirinil]esil tiofene] P[T6Br-co-T6TPP] contenenti differenti quantit�� di porfirina, sono stati sintetizzati sia con metodi non regiospecifici che regiospecifici, con lo scopo di confrontarene le propriet�� e di verificare se la strutture macromolecolare che presenta una regiochimica di sostituzione sempre uguale, promuove o meno il trasporto della carica elettrica, migliorando di conseguenza l'efficienza. E' stato inoltre effettuato un ulteriore confronto tra questi derivati e derivati simili P[T6H-co-T6TPP] che non contengono l'atomo di bromo in catena laterale con lo scopo di verificare se l'assenza del gruppo reattivo, migliora o meno la stabilit�� termica e chimica dei film polimerici, agendo favorevolmete sulle performance dei dispositivi fotovoltaici. Tutti i copolimeri sono stati caratterizzati con differenti tecniche: spettroscopia NMR, FT-IR e UV-Vis, analisi termiche DSC e TGA, e GPC. Le celle solari Bulk Heterojunction, preparate utilizzando PCBM come materiale elettron-accettore e i copolimeri come materilai elettron-donatori, sono state testate utilizzando un multimetro Keithley e il Solar Simulator.

Efficient luminescent solar concentrators based on self-absorption free, Tm2+ doped halides

The optical and luminescence properties of CaI2 and NaCl doped with divalent thulium are reported for solar energy applications. These halides strongly absorb solar light from the UV up to 900 nm due to the intense Tm2+ 4f13���4f125d1 electronic transitions. Absorption is followed by emission of 1140 nm light due to the 2F5/2���2F7/2 transition of the 4f13 configuration that can be efficiently converted to electric power by thin film CuInSe2 (CIS) solar cells. Because of a negligible spectral overlap between absorption and emission spectra, a luminescent solar concentrator (LSC) based on these black luminescent materials would not suffer from self-absorption losses. The Tm2+ doped halides may therefore lead to efficient semi-transparent power generating windows that absorb solar light over the whole visible spectrum. It will be shown that the power efficiency of the Tm2+ based LSCs can be up to four times higher compared to LSCs based on organic dyes or quantum dots.

Benthic foraminifera, stable isotope ratios and carbon concentrations of sediment cores from Propeller Mound and Porcupine Srabight

On- and off-mound sediment cores from Propeller Mound (Hovland Mound province, Porcupine Seabight) were analysed to understand better the evolution of a carbonate mound. The evaluation of benthic foraminiferal assemblages from the off-mound position helps to determine the changes of the environmental controls on Propeller Mound in glacial and interglacial times. Two different assemblages describe the Holocene and Marine Isotope Stage (MIS) 2 and late MIS 3 (~31 kyr BP). The different assemblages are related to changes in oceanographic conditions, surface productivity and the waxing and waning of the British Irish Ice Sheet (BIIS) during the last glacial stages. The interglacial assemblage is related to a higher supply of organic material and stronger current intensities in water depth of recent coral growth. During the last glaciation the benthic faunas showed high abundances of cassidulinid species, implying cold bottom waters and a reduced availability of organic matter. High sedimentation rates and the domination of Elphidium excavatum point to shelf erosion related to sea-level lowering (~50 m) and the progradation of the BIIS onto the shelf. A different assemblage described for the on-mound core is dominated by Discanomalina coronata, Gavelinopsis translucens, Planulina ariminensis, Cibicides lobatulus and to a lower degree by Hyrrokkin sarcophaga. These species are only found or show significantly higher relative abundances in on-mound samples and their maximum contribution in the lower part of the record indicates a higher coral growth density on Propeller Mound in an earlier period. They are less abundant during the Holocene, however. This dataset portrays the boundary conditions of the habitable range for the cold-water coral Lophelia pertusa, which dominates the deep-water reefal ecosystem on the upper flanks of Propeller Mound. The growth of this ecosystem occurs during interglacial and interstadial periods, whereas a retreat of corals is documented in the absence of glacial sediments on-mound. Glacial conditions with cold intermediate waters, a weak current regime and high sedimentation rates provide an unfavourable environmental setting for Lophelia corals to grow. A Late Pleistocene decrease is observed in the mound growth for Propeller Mound, which might face its complete burial in the future, as it already happened to the buried mounds of the Magellan Mound province further north.

Intermolecular and Intramolecular Charge Transfer in Functional Molecular Materials

This thesis is devoted to the investigation of inter and intramolecular charge transfer (CT) in molecular functional materials and specifically organic dyes and CT crystals. An integrated approach encompassing quantum-chemical calculations, semiempirical tools, theoretical models and spectroscopic measurements is applied to understand structure-property relationships governing the low-energy physics of these materials. Four main topics were addressed: 1) Spectral properties of organic dyes. Charge-transfer dyes are constituted by electron donor (D) and electron acceptor (A) units linked through bridge(s) to form molecules with different symmetry and dimensionality. Their low-energy physics is governed by the charge resonance between D and A groups and is effectively described by a family of parametric Hamiltonians known as essential-state models. These models account for few electronic states, corresponding to the main resonance structures of the relevant dye, leading to a simple picture that is completed introducing the coupling of the electronic system to molecular vibrations, treated in a non-adiabatic way, and an effective classical coordinate, describing polar solvation. In this work a specific essential-state model was proposed and parametrized for the dye Brilliant Green. The central issue in this work has been the definition of the diabatic states, a not trivial task for a multi-branched chromophore. In a second effort, we have used essential-state models for the description of the early-stage dynamics of excited states after ultrafast excitation. Crucial to this work is the fully non-adiabatic treatment of the coupled electronic and vibrational motion, allowing for a reliable description of the dynamics of systems showing a multistable, broken-symmetry excited state. 2) Mixed-stack CT salts. Mixed-stack (MS) CT crystals are an interesting class of multifunctional molecular materials, where D and A molecules arrange themselves to form stacks, leading to delocalized electrons in one dimension. The interplay between the intermolecular CT, electrostatic interactions, lattice phonons and molecular vibrations leads to intriguing physical properties that include (photoinduced) phase transitions, multistability, antiferromagnetism, ferroelectricity and potential multiferroicity. The standard microscopic model to describe this family of materials is the Modified Hubbard model accounting for electron-phonon coupling (Peierls coupling), electron-molecular vibrations coupling (Holstein coupling) and electrostatic interactions. We adopt and validate a method, based on DFT calculations on dimeric DA structures, to extract relevant model parameters. The approach offers a powerful tool to shed light on the complex physics of MS-CT salts. 3) Charge transfer in organic radical dipolar dyes. In collaboration with the group of Prof. Jaume Veciana (ICMAB- Barcellona), we have studied spectral properties of a special class of CT dyes with D-bridge-A structure where the acceptor group is a stable radical (of the perchlorotriphenylmethyl, PTM, family), leading to an open-shell CT dyes. These materials are of interest since they associate the electronic and optical properties of CT dyes with magnetic properties from the unpaired electron. The first effort was devoted to the parametrization of the relevant essential-state model. Two strategies were adopted, one based on the calculation of the low-energy spectral properties, the other based on the variation of ground state properties with an applied electric field. 4) The spectral properties of organic nanoparticles based on radical species are investigated in collaboration with Dr. I. Ratera (ICMAB- Barcellona). Intriguing spectroscopic behavior was observed pointing to the presence of excimer states. In an attempt to rationalize these findings, extensive calculations (TD-DFT and ZINDO) were performed. The results for the isolated dyes are validated against experimental spectra in solution. To address intermolecular interactions we studied dimeric structures in the gas phase, but the preliminary results obtained do not support excimer formation.

Mechanical, thermal and colorimetric properties of LLDPE coloured with a blue nanopigment and conventional blue pigments

Purpose ��� This research deals with a new kind of nanopigment, obtained from the combination of organic dyes and layered nanoclays, that the authors call nanoclay-colorant pigment (NCP). Whilst they have already been employed in inks and coatings, to date these nanopigments have not been used as pigments for polymers. The existing lack of knowledge surrounding them must be redressed in order to bridge the gap between current academic studies and commercial exploitation. Therefore, the main purpose of this paper is to examine the hitherto unknown aspects of the NCP, which relate specifically to their applicability as a new type of colorant for polymers. Design/methodology/approach ��� A blue NCP has been prepared at the laboratory according to the patented method of synthesis (patent WO0104216), using methylene blue and montmorillonite nanoclay. It has then been applied to a thermoplastic polymer (linear low-density polyethylene ��� LLDPE) to obtain a coloured sample. Furthermore, samples with the same polymer but using conventional blue colorants have been prepared under the same processing conditions. The mechanical, thermal and colorimetric properties of these materials have been compared. Findings ��� The thermal stability of the sample coloured with NCP is reduced to some extent, while the mechanical strength is slightly increased. Moreover, this sample has better colour performance than the conventionally pigmented samples. Originality/value ��� In this paper, a blue NCP has been synthesised and successfully employed with polyethylene and the obtained sample shows better colour performance than polyethylene with conventional pigments.

CIMBNC- Combination and interactions of three kinds of nanoclays structural modifiers, for the colored bio-nanocomposites optimization

Biopolymers do not have competitive prices, which has prevented their industrial exploitation on a global scale so far. In this context, Using nanoclays, improvements in certain biopolymer properties, mainly mechanical and thermal, have been achieved. However, research has been much less focused on changing optical properties through the incorporation of nanoclays. At the same time, current research has focused on obtaining nanopigments, by organic dyes adsoptions into different nanoclays in order to achieve sustainable colouring and high performance materials. By combining advances in these lines of research, biodegradable composites with optimal mechanical and optical properties can be obtained. The aim of this work is to find the optimal formulation of naturally sourced nanopigments, incorporate them into a biological origin epoxy resin, and obtain a significant improvement in their mechanical, and optical properties. We combine three structural modifiers in the nanopigment synthesis: surfactant, silane and mordant salt. The latter was selected in order to replicate the mordant textile dyeing with natural dyes. Using a Taguchi���s desing L8, we look for the effect of the presence of the modifiers, the pH acidification, and the interactions effect between the synthesis factors. Three natural dyes were selected: chlorophyll, beta-carotene, and beetroot extract. Furthermore we use two kinds of laminar nanoclays, differentiated by the ion exchange charge: montmorillonite, and hydrotalcite. Then the thermal, mechanical and colorimetric characterization of the bionanocomposite materials was carried out. The optimal conditions to obtain the best bionanocomposite materials are using acid pH, and modifying the nanoclays with mordant and surfactant.

Tight-Binding Approximations in 1D and 2D Coupled-Cavity Photonic Crystal Structures

Light confinement and controlling an optical field has numerous applications in the field of telecommunications for optical signals processing. When the wavelength of the electromagnetic field is on the order of the period of a photonic microstructure, the field undergoes reflection, refraction, and coherent scattering. This produces photonic bandgaps, forbidden frequency regions or spectral stop bands where light cannot exist. Dielectric perturbations that break the perfect periodicity of these structures produce what is analogous to an impurity state in the bandgap of a semiconductor. The defect modes that exist at discrete frequencies within the photonic bandgap are spatially localized about the cavity-defects in the photonic crystal. In this thesis the properties of two tight-binding approximations (TBAs) are investigated in one-dimensional and two-dimensional coupled-cavity photonic crystal structures We require an efficient and simple approach that ensures the continuity of the electromagnetic field across dielectric interfaces in complex structures. In this thesis we develop \textrm{E} -- and \textrm{D} --TBAs to calculate the modes in finite 1D and 2D two-defect coupled-cavity photonic crystal structures. In the \textrm{E} -- and \textrm{D} --TBAs we expand the coupled-cavity \overrightarrow{E} --modes in terms of the individual \overrightarrow{E} -- and \overrightarrow{D} --modes, respectively. We investigate the dependence of the defect modes, their frequencies and quality factors on the relative placement of the defects in the photonic crystal structures. We then elucidate the differences between the two TBA formulations, and describe the conditions under which these formulations may be more robust when encountering a dielectric perturbation. Our 1D analysis showed that the 1D modes were sensitive to the structure geometry. The antisymmetric \textrm{D} mode amplitudes show that the \textrm{D} --TBA did not capture the correct (tangential \overrightarrow{E} --field) boundary conditions. However, the \textrm{D} --TBA did not yield significantly poorer results compared to the \textrm{E} --TBA. Our 2D analysis reveals that the \textrm{E} -- and \textrm{D} --TBAs produced nearly identical mode profiles for every structure. Plots of the relative difference between the \textrm{E} and \textrm{D} mode amplitudes show that the \textrm{D} --TBA did capture the correct (normal \overrightarrow{E} --field) boundary conditions. We found that the 2D TBA CC mode calculations were 125-150 times faster than an FDTD calculation for the same two-defect PCS. Notwithstanding this efficiency, the appropriateness of either TBA was found to depend on the geometry of the structure and the mode(s), i.e. whether or not the mode has a large normal or tangential component.

Estudo comparativo dos processos eletroqu��micos oxidativos avan��ados (PEOAs) no tratamento de efluentes contendo corantes org��nicos de dif��cil degrada����o

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ���OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Estudo comparativo dos processos eletroqu��micos oxidativos avan��ados (PEOAs) no tratamento de efluentes contendo corantes org��nicos de dif��cil degrada����o

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ���OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Near-field coupling and resonant cavity modes in plasmonic nanorod metamaterials

Plasmonic resonant cavities are capable of confining light at the nanoscale, resulting in both enhanced local electromagnetic fields and lower mode volumes. However, conventional plasmonic resonant cavities possess large Ohmic losses at metal-dielectric interfaces. Plasmonic near-field coupling plays a key role in a design of photonic components based on the resonant cavities because of the possibility to reduce losses. Here, we study the plasmonic near-field coupling in the silver nanorod metamaterials treated as resonant nanostructured optical cavities. Reflectance measurements reveal the existence of multiple resonance modes of the nanorod metamaterials, which is consistent with our theoretical analysis. Furthermore, our numerical simulations show that the electric field at the longitudinal resonances forms standing waves in the nanocavities due to the near-field coupling between the adjacent nanorods, and a new hybrid mode emerges due to a coupling between nanorods and a gold-film substrate. We demonstrate that this coupling can be controlled by changing the gap between the silver nanorod array and gold substrate.

Photoacoustic tomography: principles and advances.

Photoacoustic tomography (PAT) is an emerging imaging modality that shows great potential for preclinical research and clinical practice. As a hybrid technique, PAT is based on the acoustic detection of optical absorption from either endogenous chromophores, such as oxy-hemoglobin and deoxy-hemoglobin, or exogenous contrast agents, such as organic dyes and nanoparticles. Because ultrasound scatters much less than light in tissue, PAT generates high-resolution images in both the optical ballistic and diffusive regimes. Over the past decade, the photoacoustic technique has been evolving rapidly, leading to a variety of exciting discoveries and applications. This review covers the basic principles of PAT and its different implementations. Strengths of PAT are highlighted, along with the most recent imaging results.

Tight-Binding Approximations in 1D and 2D Coupled-Cavity Photonic Crystal Structures

Light confinement and controlling an optical field has numerous applications in the field of telecommunications for optical signals processing. When the wavelength of the electromagnetic field is on the order of the period of a photonic microstructure, the field undergoes reflection, refraction, and coherent scattering. This produces photonic bandgaps, forbidden frequency regions or spectral stop bands where light cannot exist. Dielectric perturbations that break the perfect periodicity of these structures produce what is analogous to an impurity state in the bandgap of a semiconductor. The defect modes that exist at discrete frequencies within the photonic bandgap are spatially localized about the cavity-defects in the photonic crystal. In this thesis the properties of two tight-binding approximations (TBAs) are investigated in one-dimensional and two-dimensional coupled-cavity photonic crystal structures We require an efficient and simple approach that ensures the continuity of the electromagnetic field across dielectric interfaces in complex structures. In this thesis we develop \textrm{E} -- and \textrm{D} --TBAs to calculate the modes in finite 1D and 2D two-defect coupled-cavity photonic crystal structures. In the \textrm{E} -- and \textrm{D} --TBAs we expand the coupled-cavity \overrightarrow{E} --modes in terms of the individual \overrightarrow{E} -- and \overrightarrow{D} --modes, respectively. We investigate the dependence of the defect modes, their frequencies and quality factors on the relative placement of the defects in the photonic crystal structures. We then elucidate the differences between the two TBA formulations, and describe the conditions under which these formulations may be more robust when encountering a dielectric perturbation. Our 1D analysis showed that the 1D modes were sensitive to the structure geometry. The antisymmetric \textrm{D} mode amplitudes show that the \textrm{D} --TBA did not capture the correct (tangential \overrightarrow{E} --field) boundary conditions. However, the \textrm{D} --TBA did not yield significantly poorer results compared to the \textrm{E} --TBA. Our 2D analysis reveals that the \textrm{E} -- and \textrm{D} --TBAs produced nearly identical mode profiles for every structure. Plots of the relative difference between the \textrm{E} and \textrm{D} mode amplitudes show that the \textrm{D} --TBA did capture the correct (normal \overrightarrow{E} --field) boundary conditions. We found that the 2D TBA CC mode calculations were 125-150 times faster than an FDTD calculation for the same two-defect PCS. Notwithstanding this efficiency, the appropriateness of either TBA was found to depend on the geometry of the structure and the mode(s), i.e. whether or not the mode has a large normal or tangential component.

Fabrication, Optical Analysis and Photonic Applications of Certain Metallic Nanostructure-Integrated Dye Doped Polymer Optical Fibers��� submitted by Ms. Suneetha Sebastian

Polymer Optical Fibers have occupied historically a place for large core flexible fibers operating in short distances. In addition to their practical passive application in short-haul communication they constitute a potential research field as active devices with organic dopants. Organic dyes are preferred as dopants over organic semiconductors due to their higher optical cross section. Thus organic dyes as gain media in a polymer fiber is used to develop efficient and narrow laser sources with a tunability throughout the visible region or optical amplifier with high gain. Dyes incorporated in fiber form has added advantage over other solid state forms such as films since the pump power required to excite the molecules in the core of the fiber is less thereby utilising the pump power effectively. In 1987, Muto et.al investigated a dye doped step index polymer fiber laser. Afterwards, numerous researches have been carried out in this area demonstrating laser emission from step index, graded index and hollow optical fibers incorporating various dyes. Among various dyes, Rhodamine6G is the most widely and commonly used laser dye for the last four decades. Rhodamine6G has many desirable optical properties which make it preferable over other organic dyes such as Coumarin, Nile Blue, Curcumin etc. The research focus on the implementation of efficient fiber lasers and amplifiers for short fiber distances. Developing efficient plastic lasers with electrical pumping can be a new proposal in this field which demands lowest possible threshold pump energy of the gain medium in the cavity as an important parameter. One way of improving the efficiency of the lasers, through low threshold pump energy, is by modifying the gain of the amplifiers in the resonator/cavity. Success in the field of Radiative Decay Engineering can pave way to this problem. Laser gain media consisting of dye-nanoparticle composites can improve the efficiency by lowering the lasing threshold and enhancing the photostability. The electric field confined near the surface of metal nanoparticles due to Localized Surface Plasmon Resonance can be very effective for the excitation of active centers to impart high optical gain for lasing. Since the Surface Plasmon Resonance of nanoparticles of gold and silver lies in the visible range, it can affect the spectral emission characteristics of organic dyes such as Rhodamine6G through plasmon field generated by the particles. The change in emission of the dye placed near metal nanoparticles depend on plasmon field strength which in turn depends on the type of metal, size of nanoparticle, surface modification of the particle and the wavelength of incident light. Progress in fabrication of different types of nanostructures lead to the advent of nanospheres, nanoalloys, core-shell and nanowires to name a few. The thesis deals with the fabrication and characterisation of polymer optical fibers with various metallic and bimetallic nanostructures incorporated in the gain media for efficient fiber lasers with low threshold and improved photostability.

Three-dimensional fluorescence characteristics of dissolved organic matter produced by Prorocentrum donghaiense Lu

Filtration and cross-flow ultrafiltration techniques were used to separate culture media of Prorocentrum donghaiense at the exponential growth, stationary and decline stages into < 0.45 mu m filtrate, 100 kDa-0.45 mu m, 10-100 kDa and 1-10 kDa retentate and < 1 kDa ultrafiltrate fractions. The fluorescence. properties of different molecular weights of dissolved organic matter (DOM) were measured by excitation-emission matrix spectra. Protein-like and humic-like fluorophores were observed in the DOM produced by P. donghaiense. The central positions of protein-like fluorophores showed a red shift with prolonged growth duration, shifting from tyrosine-like properties at the exponential growth stage to tryptophan-like properties at the stationary and decline stages. The excitation wavelengths of protein-like fluorophores exhibited some change in the exponential growth and stationary stages with increased molecular size, but showed little change in the decline stage. However, the emission wavelengths in the decline stage exhibited a blue shift. Very distinct C type and A type peaks in humic-like fluorophores were observed. With a prolonged culture time, the intensities of both of the peaks became strong and the excitation wavelengths of peak A showed a red shift, while the A:C ratios fell. More than 94% of fluorescent DOM was in the lower than 1 kDa molecular weight fraction.